Understanding Electrode Potentials: Why is 1/Molarity Used in the Calculation?

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SUMMARY

The calculation of electrode potential for a silver-filled electrode in a 0.00550 M AgNO3 solution utilizes the Nernst equation. The electrode potential is determined using the formula E = E* - 0.0592 log(1/[Ag+]), resulting in E = 0.6655 V. The inverse concentration (1/[Ag+]) is used because the Nernst equation accounts for the activity of the oxidized form, Ag+, in relation to the reduced form, Ag(s). Understanding the two conventions of the Nernst equation is crucial for accurate calculations.

PREREQUISITES
  • Understanding of the Nernst equation and its applications
  • Familiarity with electrochemical cells and electrode potentials
  • Knowledge of silver ion chemistry and its reduction to metallic silver
  • Basic logarithmic calculations in chemistry
NEXT STEPS
  • Study the Nernst equation in detail, focusing on both conventions
  • Explore the concept of electrode potentials in electrochemical cells
  • Learn about the significance of ion activity in electrochemistry
  • Investigate the effects of concentration changes on electrode potential
USEFUL FOR

Chemistry students, electrochemists, and anyone involved in analytical chemistry or electrochemical research will benefit from this discussion.

Puchinita5
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I don't know why, but I just can't figure this out.

"Calculate the electrode potential for a silver filled electrode in a solution of 0.00550 M AgNO3 solution."

I got that

Ag+ + e- --> Ag(s) had an E* = .80V

I got that the answer is E=.80 - .0592 log (1/.00550M)= .6655 V

But why do you put 1/.00550M in the parenthesis?

My first thought was that AgNO3 + e- --> Ag(s) + NO3-
and that the concentreation of AgNO3 is the same as NO3.

so that it would be log(1) , which is wrong.

I just don't get the concept I guess.
 
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It all depends on how you write the Nernst equation. There are two conventions:

E = E_0 + \frac {RT}{nF} ln \frac{[Ox]}{[Red]}

and

E = E_0 - \frac {RT}{nF} ln \frac{[Red]}{[Ox]}

(personally I prefer the first one, but that's just because I was taught this way).

Note that both equations are equivalent thanks to the sign change.

Oxidized form of silver is Ag+, reduced form is a metallic Ag - with activity equal to 1. So you can write the equation either as

E = 0.88 + 0.059\ log([Ag^+])

or

E = 0.88 - 0.059\ log\big(\frac 1 {[Ag^+]}\big)

Concentration of Ag+ is 0.00550 M, concentration of NO3- doesn't matter.
 
oh! okay that makes sense. I don't know why but I always confuse myself with these electrode problems.

Thank you!
 

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